Material compositions and sequences of manufacturing

ABSTRACT

The disclosure provides for a valve including a surface movably engaged with another surface. A coating is on the surface and is characterized by: a CoF of less than 0.1; a hardness in excess of 1,200 HVN; impermeability to liquids at pressures ranging from 15 and 20,000 psi; a surface finish of 63 or less; and a thickness ranging from 0.5 to 20 mils. The disclosure provides for material constructions including a continuous phase, including a transition metal, and a discontinuous phase, including a solid dry lubricant. The disclosure also provides for a method of depositing a coating that includes depositing a first layer of a coating onto a surface using electroplating, electroless plating, thermal spraying, or cladding, and then depositing a second layer of the coating onto a surface of the first layer using sputtering, ion beam, plasma enhanced chemical vapor deposition, cathodic arc, or chemical vapor deposition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.16/183,388, filed on Nov. 7, 2018, which is incorporated herein byreference in its entirety.

FIELD

The present disclosure relates to hard and lubricious valve surfaces,hard and lubricious material compositions, apparatus and systemsincluding the same, and to methods of making and using the same,including sequences of manufacturing the same.

BACKGROUND

Components that, when in operation, have contacting surfaces that are inrelative motion typically experience abrasive wear on the surfacescaused by the frictional engagement therebetween. Such components mayalso experience corrosion, particularly when operating under relativelyharsh conditions, such as in various oil and gas exploration, drilling,and production environments. Examples of such harsh conditions includethose having sour or H₂S-containing gases under high-partial pressures,high-chloride concentrations (high salinity) above ambient temperature,high-CO₂ partial pressures, and combinations of these conditions.Additional examples of harsh conditions include warm and oxygenatedaqueous environments, as are especially encountered when continuouslyinjecting untreated seawater in an underground reservoir. Theseconditions are considered harsh because they are corrosive to typicalmetallic materials and can lead to various forms of degradation overtime, including loss of thickness, pitting, crevices, cracking understatic and/or cyclic stress, which are all potential causes ofuncontrolled loss of fluids through sealing surfaces or metallic walls.

Some such components that are often operated in harsh environments arevalves, including ball valves. These ball valves may be positioned atsurface, subsea, and/or downhole, in all cases serving a similarfunction of flow and/or pressure control. Ball valves use a hollow,perforated and pivoting ball to control fluid flow therethrough.Typically, in the open position the hole through the ball is alignedwith the fluid flow, and in the closed position the ball is pivoted by90° relative to the open position such that the hole through the ball isout of alignment with the fluid flow. Other valves that are oftenoperated in harsh environments, and may include linear perforatedpistons as an alternative to ball/seat assemblies, include flow controlvalves, safety valves, formation isolation valves, and subsea lubricatorvalves. Flow control valves are typically used in completion toselectively control multiple zones, and downhole safety valves are usedto provide for emergency closure in wellbores. These two types of valvesare usually actually actuated by hydraulic pressure, occasionally viaelectrical actuations, are cylindrical, and typically utilize linearpiston tubes, either selectively perforated to allow radial flow ornon-perforated to directly actuate a flapper. Formation isolation valvesare typically ball valves used to isolate reservoir fluids, andlubricator valves, including subsea lubricator valves, are the topmostvalve on a Christmas tree that provides access to a wellbore. Each ofthese valves includes surfaces that move relative to one another, whichsubjects these surfaces to wear or various forms of degradation.

BRIEF SUMMARY

One aspect of the present disclosure includes a flow control valve. Thevalve includes a first surface movably engaged with a second surface. Acoating is on the first surface. The coating includes at least a firstlayer. The coating is characterized by: a coefficient of friction ofless than 0.15 in dry condition; a hardness in excess of 1,200 HVN;impermeability to liquids at pressures ranging from 15 and 20,000 psi; asurface finish of 63 or less; and a thickness ranging from 0.5 to 20mils.

Another aspect of the present disclosure includes a materialconstruction. The material construction includes a first layer. Thefirst layer includes at least two immiscible phases, including from 70to 99 volume percent of a continuous phase and from 1 to 30 volumepercent of a discontinuous phase dispersed within the continuous phase,each based on a total volume of the first layer. The discontinuous phaseincludes a solid dry lubricant. The continuous phase includes Ni and Coin an amount ranging from 50 to 70 wt. %, Cr in an amount ranging from16 wt. % to 30 wt. %, Mo in an amount ranging from 2.5 wt. % to 10 wt.%, W in an amount ranging from 0 wt. % to 4 wt. %, and Fe in an amountranging from 0 wt. % to 15 wt. %, each based on a total weight of thecontinuous phase.

Another aspect of the present disclosure includes a method of depositinga coating onto a surface of a valve. The method includes depositing afirst layer of a coating onto a surface of a valve. The first layer isdeposited using electroplating, electroless plating, thermal spraying,or cladding. The method includes depositing a second layer of thecoating onto a surface of the first layer. The second layer is depositedusing one of the same process as the first layer, or sputtering, ionbeam, plasma enhanced chemical vapor deposition, cathodic arc, orchemical vapor deposition. The second layer may be optional and mayinclude a sub-layer.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the features of the compositions, articles,systems and methods of the present disclosure may be understood in moredetail, a more particular description briefly summarized above may behad by reference to the embodiments thereof which are illustrated in theappended drawings that form a part of this specification. It is to benoted, however, that the drawings illustrate only various exemplaryembodiments and are therefore not to be considered limiting of thedisclosed concepts as it may include other effective embodiments aswell.

FIG. 1 depicts a monolayer coating applied to an apparatus, inaccordance with certain aspects of the present disclosure.

FIG. 2 depicts a multilayer (bilayer) coating applied to an apparatus,in accordance with certain aspects of the present disclosure.

FIG. 3 depicts two monolayer coatings applied to two surfaces that aremovably engaged, in accordance with certain aspects of the presentdisclosure.

FIG. 4 depicts a monolayer coating applied to a surface that is movablyengaged with another surface that is uncoated, in accordance withcertain aspects of the present disclosure.

FIG. 5 depicts an exemplary multiphasic material composition suitablefor use in at least one layer of the coatings, in accordance withcertain aspects of the present disclosure.

FIG. 6 depicts a multilayer (tri-layer) coating applied to an apparatus,in accordance with certain aspects of the present disclosure.

FIG. 7 depicts a ball valve including a surface having a coating appliedthereto, in accordance with certain aspects of the present disclosure.

FIGS. 8A-8D depict an uncoated apparatus being sequentially treated toform a coated apparatus, in accordance with certain aspects of thepresent disclosure.

FIG. 9 depicts a three-layer material construction, in accordance withcertain aspects of the present disclosure.

FIG. 10A is an exemplary, high magnification electron micrograph of atop view showing the surface structure of a coating at the submicronscale, in accordance with the present disclosure.

FIG. 10B is an exemplary, high magnification electron micrograph side,cross-sectional view of the coating of FIG. 10A showing the two layersof the coating.

Compositions, articles, systems, and methods according to presentdisclosure will now be described more fully with reference to theaccompanying drawings, which illustrate various exemplary embodiments.Concepts according to the present disclosure may, however, be embodiedin many different forms and should not be construed as being limited bythe illustrated embodiments set forth herein. Rather, these embodimentsare provided so that this disclosure will be thorough as well ascomplete and will fully convey the scope of the various concepts tothose skilled in the art and the best and preferred modes of practice.

DETAILED DESCRIPTION

The present disclosure provides for hard and lubricious materialcompositions; apparatus and systems, such as valve surfaces, includingthe same; and to methods of making and using the same, includingsequences of manufacturing the same.

In certain aspects, the present disclosure provides for improvements inthe performance of apparatus (e.g., valves and other components) thatare subjected to corrosive, abrasive and/or otherwise relatively harshoperating conditions. Such improved performance is attained by modifyingand/or treating the apparatus or the surface thereof to have desiredsurface characteristics. The surface characteristics include, but arenot limited to, lubricity, hardness, inertness, or combinations thereof.Each of lubricity, hardness and inertness may at least partially providean apparatus with various performance enhancements such as a longerlifespan (extended service capabilities), elimination or reduction ofleak paths and leak rates, and other performance enhancements. In thecontext of this disclosure, the term inertness is synonymous with anelevated general corrosion resistance, including the absence of anyperceived participation in any chemical or electrochemical reactionbetween the material composition and surrounding fluid in the conditionsof use. A layer is formed typically by a single individual processwithin an fixed equipment in a fixed set-up or fixture. A sub-layer maybe formed as part of such process within a fixed equipment in a fixedset-up or fixture. A typical sublayer may include new chemistries, ormixed chemistries between the base material or part and the subsequentlayer. While sublayers are not detailed herein, one skilled in the artwould understand that such sublayers may be utilized in the materialconstructions disclosed herein to modify the coating performance.

Material Compositions and Constructions

Certain aspects of the present disclosure include material compositions,constructions and arrangements, and applications thereof onto surfacesthat are movably engaged (i.e., surfaces that are in contact and moverelative to one another during operation of the apparatus). The materialconstructions may be in the form of coatings or films applied to atleast one of the surfaces that are movably engaged. With reference toFIG. 1, exemplary coated surface 100 is depicted. Coated surface 100includes coating 110 applied to surface 112 of apparatus 114. Apparatus,or surface 112 thereof, may be composed of any of various materialsincluding, but not limited to, carbon steel, low-alloy-steel, stainlesssteel, or a superalloy (e.g., a superalloy of nickel or cobalt). Whileshown and described herein as a coating, the material constructiondisclosed herein is not limited to being in the form of a coating.Coating 110 is a monolayer coating, including a single coating layer116, having a thickness 111. However, the coatings disclosed herein arenot limited to monolayer coatings, and may include multilayer coatings,such as coating 210 shown in FIG. 2. Throughout the present disclosure,like (but modified) reference numerals indicate like parts. For example,in FIG. 1 the coated surface is identified via reference numeral 100,while in FIG. 2 the coated surface is identified via reference numeral200. Coated surface 200 is substantially identical, in arrangement, tocoated surface 100, with the exception that coating 210 is a bilayercoating, including coating layer 216 a applied to surface 212 ofapparatus 214 and coating layer 216 b applied to surface 218 of coatinglayer 216 a. Coating layer 216 b has thickness 213.

Surface 112 or 212 of apparatus 114 or 214 may be a surface that istypically in moving contact with another surface, such as a surface on amovable portion of valve (e.g., the ball of a ball valve). As such, thecoatings, or other forms of the material composition, disclosed hereinmay provide a protective barrier to the underlying surface of theparticular apparatus.

As shown in FIG. 3, each surface that is in moving contact may be coatedwith either a coating in accordance with the present disclosure oranother coating. FIG. 3 depicts coated surface 300 a in moving contactwith coated surface 300 b. Surface 318 a of coating 310 a is shownslightly separated from surface 318 b of coating 310 b for the purposeof clarity; however, one skilled in the art would understand that,during operation, surfaces 318 a and 318 b may be in at least partialcontact while moving relative to one another. While apparatus 314 a and314 b are shown and described as different apparatus, apparatus 314 aand 314 b may be different surfaces of a single apparatus.

As shown in FIG. 4, in some aspects only one of the surfaces that is inmoving contact may be coated with either a coating in accordance withthe present disclosure or another coating. FIG. 4 depicts coated surface400, including coating 410 on apparatus 414 a. Surface 418 is in movingcontact with surface 412 of uncoated apparatus 414 b. Surface 418 ofcoating 410 is shown slightly separated from surface 412 of apparatus414 b for the purpose of clarity; however, one skilled in the art wouldunderstand that, during operation, surfaces 418 and 412 may be in atleast partial contact while moving relative to one another. As discussedin more detail elsewhere herein, apparatus 114, 214, 314 a, 314 b, 414a, and 414 b may be any of numerous apparatus that, when in operation,have surfaces in moving contact with one another or with a surface ofanother apparatus.

Material Composition and Coating Properties

The coatings or other material constructions disclosed herein mayexhibit and/or cause the surfaces to which the coatings are applied toexhibit one or more physical, mechanical, and/or chemical properties orcharacteristics, including surface properties or characteristics.

The coatings (or other material constructions) disclosed herein may beinert and/or cause the surfaces to which the coatings are applied to beinert. In some such aspects, the material composition (and coatings andconstructions thereof) are sufficiently inert such that the compositionis corrosion resistance or substantially corrosion resistant. Forexample, a valve surface having a coating in accordance with the presentdisclosure applied thereon may exhibit corrosion resistance whenoperating in relatively harsh and/or high temperature environments, suchas when operating in a downhole or subsea environment with corrosivefluids flowing therethrough or otherwise in contact therewith. Incertain aspects, the coatings and/or surfaces to which the coatings areapplied exhibit a corrosion resistance that is equal to or greater thanthe corrosion resistance exhibited by tungsten carbide (WC) spraycoatings that contain 10 wt. % Co and 4 wt. % Cr, such as AMDRY® 5843,WOKA® 3903, PMET 86-10-4 (Polymet), among others, which are used inflow-control valves and may constitute a reference or benchmark that islimited by operations in harsh environments. One skilled in the artwould understand that there are numerous standards for measuringcorrosion resistance, including a salt spray test, such as in accordancewith ASTM B-117 Salt Spray/Salt Fog.

The coatings (or other material constructions) disclosed herein mayexhibit lubricity and/or cause the surfaces to which the coatings areapplied to exhibit lubricity. The lubricity provided by the materialcompositions and constructions herein may be sufficient to provide forlow-friction engagement between two surfaces, where at least one of thesurfaces has the material composition and construction thereon. Forexample, the lubricity provided by the material compositions andconstructions disclosed herein may provide for ease of valve actuation.In some such aspects, the coatings (or other material constructions)and/or surfaces to which the coatings are applied exhibit a kineticcoefficient of friction (CoF) of less than 0.15, or less than 0.04, orfrom 0.04 to 0.15, when measured with both surfaces in a dry condition.For example, coatings applied to valve seats and/or valve rings mayexhibit a CoF of less than 0.15, and coatings applied to bearings mayexhibit a CoF of less than 0.07. As such, the material compositionsdisclosed herein will reduce the actuation torque required to actuate avalve (e.g., the force required to open a linear valve, such as downholeflow control valve). CoF may be measured in accordance with ASTM G99-17,Standard Test Method for Wear Testing with a Pin-on-Disk Apparatus,using a stainless-steel pin. CoF measurements disclosed herein werederived from the average of measurements over a 20 min test duration.

The coatings (or other material constructions) disclosed herein mayexhibit hardness and/or cause the surfaces to which the coatings areapplied to exhibit hardness. For example, such coatings or surfaces mayexhibit a hardness equal to or in excess of 1200 Hardness Vickers Number(HVN). For example, certain aspects provide for a ball or seat of avalve (e.g., a ball valve) having a hardness in excess of 1200 HVN. Aswould be understood by one skilled in the art, HVN may be determined inaccordance with ASTM E384-17 or ISO 6507-1. Hardness provides surfaces,and the underlying apparatus, with erosion-resistance andwear-resistance, such as abrasive wear resistance, including scratchresistance. Hardness also results in surfaces, and underlying apparatus,having eliminated or at least reduced leak paths.

The coatings (or other material constructions) disclosed herein mayexhibit relatively high adhesion properties. In certain aspects, suchcoatings exhibit adhesion that is equal to or greater than the adhesionexhibited by high velocity oxygen fuel (HVOF) sprayed tungsten carbidecoatings. For example, in some such aspects, such coatings or surfacesexhibit a bond strength of equal to or greater than 10 ksi. Therelatively high adhesion properties of the coatings provide the coatingswith minimal elongation under load. In certain aspects, the coatingsexhibit an elongation in excess of 0.2%. ASTM C633-13(2017): StandardTest Method for Adhesion or Cohesion Strength of Thermal Spray Coatingsis one exemplary method for measuring adhesion. For elongation ofmaterials, ASTM E8: Standard Test Methods for Tension Testing ofMetallic Materials is one exemplary testing method.

The coatings (or other material constructions) disclosed herein may beimpermeable, or substantially impermeable, to liquids at pressuresranging from 1 atm and 20,000 psi, or 1 psi to 20,000 psi, or 10 psi to19,000 psi, or 100 psi to 18,000 psi, or 1,000 psi to 17,000 psi, or5,000 psi to 15,000 psi, or 10,000 psi to 12,000 psi. In some aspects,in order not to permeate and allow corrosive fluid through the coatingand thereunder, the coatings herein present no interconnected porosityand, in some aspects, are pore-free or substantially pore-free at themacro- and micron scale. While not limiting, one ASTM standard that maybe used in determining porosity is ASTM E2109-01(2014): Standard TestMethods for Determining Area Percentage Porosity in Thermal SprayedCoatings.

In some such aspects, the coatings (or other material constructions)disclosed herein have a thickness that is sufficient to provide thecoatings with impermeability to liquids at such pressures. The thicknessof the coatings may be sufficient to reduce or eliminate the presence ofdefects, such as porosity (holidays) and cracks (includinginterconnected cracks). The coatings may have a thickness (e.g.,thickness 111 in FIG. 1) ranging from 0.4 to 15 mils, or of at least 0.5mils, or from 1 to 10 mils, or from 1 to 8 mils, or from 2 to 6 mils, orfrom 3 to 5 mils, or of at most 10 mils. For example, a coating appliedto a ball or seat of a ball valve may have a thickness of up to 6 mil,or up to 10 mils, or from 6 to 10 mils. A coating applied to a bearingmay have a thickness of 1 mil or at least 1 mil. While not limiting,thickness may be measured by methods, including those that aredestructive to the coating. One such method includes ASTMD4138-07a(2017): Standard Practices for Measurement of Dry FilmThickness of Protective Coating Systems by Destructive, Cross-SectioningMeans. Another method is ASTM D7091 Practice for NondestructiveMeasurement of Dry Film Thickness of Nonmagnetic Coatings Applied toFerrous Metals and Nonmagnetic, Nonconductive Coatings Applied toNon-Ferrous Metals.

The coatings (or other material constructions) disclosed herein have asurface finish of 63 or less, 50 or less, or 40 or less μin. As would beunderstood by one skilled in the art, surface finish may be measuredwith a contact profilometer (stylus), non-contact profilometer (scanninginterferometry, confocal microscopy, scanning laser microscope), or avariety of other methods. While not limiting, surface finish may bemeasured using ASTM A480, ASME B46.1-2002, ISO 4287, and ISO 4288.

The material compositions and coatings (or other material constructions)disclosed herein may, macroscopically, exhibit relatively highuniformity in both the chemical and physical properties exhibitedthereby. Thus, the chemical and physical properties exhibited by thematerial compositions and coatings (or other material constructions) maybe invariant or substantially invariant over the entire surface areathereof and/or throughout the entire volume thereof. For example, theinertness, lubricity, hardness, adhesion properties, impermeability,thickness, and/or surface finish of the coatings may be invariant overthe entire surface area thereof and/or throughout the entire volumethereof.

Coatings—Monolayer

Certain aspects of the disclosure include monolayer coatings, materialcompositions thereof, apparatus coated therewith, and methods of making,applying, and using the same.

In some such aspects, the single layer of the coating, such as coatinglayer 116 of FIG. 1, includes at least two distinct and immisciblephases or components. FIG. 5 depicts an exemplary monolayer coating 510having two distinct and immiscible phases, including continuous phase520 (binder phase) and discontinuous phase 530 (dispersed phase). Whilediscontinuous phase 530 is shown as distributed throughout continuousphase 520 in a substantially random arrangement, in some aspects,discontinuous phase 530 is evenly distributed throughout continuousphase 520, such that spacing between particles of discontinuous phase530 is consistent or substantially consistent through continuous phase520.

The discontinuous, granular phase 530 of coating 510 may have a particlesize ranging from 0.5 to 150 μm, or from 1 to 100 μm, or from 10 to 80μm, or from 30 to 70 μm, or combinations of these with resultingparticle distributions being modal or bi-modal. The discontinuous,granular phase 530 may be present in the coating layer in an amountranging from 1 to 30 volume percent, or 5 to 25 volume percent, or from10 to 15 volume percent, based on the total volume of the coating layer.The discontinuous phase may include more than a single type, shape, orchemistry of embedded particles. Discontinuous phase 530 most typicallyinclude a solid dry lubricant with function to decrease friction. Thus,in some such aspects, the continuous phase of the monolayer coating maybe present in the coating layer in an amount ranging from 70 to 99volume percent, or 75 to 95 volume percent, or from 85 to 90 volumepercent, based on the total volume of the coating layer. In someaspects, the particles or grains of the discontinuous phase 530 have anaspect ratio of from 1 (e.g., for spherical, cubic, etc. shapedparticles or grains) to 100 (e.g., for cylindrical or rolling fibershaped particles or grains).

Continuous phase 520 may be or include a predominant, transition-metalbinder phase that is characterized as an electrically fullyinterconnected phase of coating 510 to result in electrically conductivecoating. An “electrically fully interconnected phase” may be a phasecapable of conducting an electrical current, where discontinuities withnon-conductive phases are absent or substantially absent. Continuousphase 520 may have a single or predominately single-phase material. Insome such aspects, continuous phase 520 may have a crystallinestructure, such as a face-centered cubic structure. Continuous phase 520may be or include Ni, Co, Cr, Mo, W, Fe, or combinations thereof. Ni andCo, combined, may be present in continuous phase 520 in an amount thatis equal to or greater than 50 wt. %, or from 50 to 70 wt. %, or from 55to 65 wt. %, or equal to or less than 70 wt. %, each based on the totalweight of continuous phase 520. Cr may be present in continuous phase520 in an amount that is equal to or greater than 16 wt. %, or from 16wt. % to 30 wt. %, or from 20 wt. % to 25 wt. %, or equal to or lessthan 30 wt. %, each based on the total weight of continuous phase 520.Mo may be present in continuous phase 520 in an amount that is equal toor greater than 2.5 wt. %, or from 2.5 wt. % to 10 wt. %, or from 4 wt.% to 8 wt. %, or from 5 wt. % to 6 wt. %, or equal to or less than 10wt. %, each based on the total weight of continuous phase 520. W may bepresent in continuous phase 520 in an amount that is equal to or lessthan 4.0 wt. %, or from 0 wt. % to 4 wt. %, or from 1 wt. % to 3 wt. %,or from 1.5 wt. % to 2.5 wt. %, or equal to or greater than 0 wt. %,each based on the total weight of continuous phase 520. Fe may bepresent in continuous phase 520 in an amount that is equal to or lessthan 15.0 wt. %, or from 0 wt. % to 15 wt. %, or from 1 wt. % to 12 wt.%, or from 2 wt. % to 10 wt. %, or equal to or greater than 0 wt. %,each based on the total weight of continuous phase 520. One skilled inthe art would understand that other elements may be present withincontinuous phase 520, whether intentional or unintentional, including intrace amounts. In some such aspects, the composition of continuous phase520 satisfies the following pitting resistance equivalent number (PREN)value rule: 1 wt. % Cr+3.3% Mo+0.5% W+16N≥30; where the value of “30” isset by critical pitting correlation for stainless steels, not Ni-richalloys, with the criteria that no pitting occurs at ambient temperatureas a lower boundary condition. For nickel alloys, a minimum PREN valueof 30 corresponds to minimum critical pitting temperature ofapproximately 30° C. as measured by ASTM G48 in 6% FeCl₃ solution, andthis PREN is approximately suitable for many applications involvingde-aerated seawater.

Solid Lubricants

In some aspects, the material composition disclosed herein includessolid lubricants, including layered thin-films and/or particulates ofsolid lubricants. Thus, solid lubricants may form a part of a compositematerial or coating in accordance with the present disclosure. In someaspects, solid lubricants are present in a layer as an additive to thatlayer, while in other aspects the solid lubricants form the bulk orentirety of the coating layer. Solid lubricants suitable for use in thepresent disclosure include, but are not limited to, soft metals;transition metal dichalcogenides; oxides, including binary oxides andternary oxides; alkaline-earth fluorides; boron nitride (hexagonal boronnitride, hBN); MAX phases; carbon or carbon-based materials; orcombinations thereof.

Soft metals suitable for use as solid dry lubricants herein include, butare not limited to, Ag, Pb, Au, In, Cu, and alloys thereof. Such softmetals may be present within a coating layer or material composition inan amount of at least 5 wt. %, or from 5 to 30 wt. %, or from 10 to 25wt. %, or at most 30 wt. %, each based on the total weight of thecoating layer or material composition. As many soft metals aresusceptible to general corrosion, and may be costly, careful selectionof soft metals is desirable.

Transition metal dichalcogenides (TMDs) suitable for use as solid drylubricants herein include, but are not limited to, MoS₂, WS₂, and MoSe₂.Such TMDs may be present within a coating layer or material compositionin an amount of at least 5 wt. % based on the total weight of thecoating layer or material composition. Several of these sulfidesdisclosed herein are effective in reducing friction in dry conditions,as well as conditions where water is present as minority phase in theflow.

Binary oxides suitable for use as solid dry lubricants herein include,but are not limited to, PBO, MoO₃, WO₃, CuO, V₂O₅, Re₂O₇, B₂O₃, Al₂O₃,ZrO₂, Fe₂O₃, FeO, and MgO. Such binary oxides may be present within acoating layer or material composition in an amount of at least 5 wt. %,or from 5 to 35 wt. %, or from 10 to 30 wt. %, or from 15 to 25 wt. % orat most 35 wt. %, each based on the total weight of the coating layer ormaterial composition. At least some of these oxides disclosed hereinoffer benefits under high-load applications; and at least some theoxides disclosed herein are reactive to water and therefore limited toapplications where water is absent or a minority phase.

Ternary oxides suitable for use as solid dry lubricants herein include,but are not limited to, Ag₂MoO₄, Ag₂WO₄, and Ag₃VO₄. Such ternary oxidesmay be present within a coating layer or material composition in anamount of at least 5 wt. %, or from 5 to 35 wt. %, or from 10 to 30 wt.%, or from 15 to 25 wt. % or at most 35 wt. %, each based on the totalweight of the coating layer or material composition.

Alkaline-earth fluorides suitable for use as solid dry lubricants hereininclude, but are not limited to, CaF₂ and BaF₂.

Boron nitrides suitable for use as solid dry lubricants herein include,but are not limited to, hexagonal boron nitride (hBN). Such boronnitrides may be present within a coating layer or material compositionin an amount of at least 5 wt. %, or from 5 to 50 wt. %, or from 10 to45 wt. %, or from 15 to 40 wt. %, or from 20 to 35 wt. %, or from 25 to30 wt. %, or from 35 to 50 wt. %, or at most 35 wt. %, or at most 50 wt.%, each based on the total weight of the coating layer or materialcomposition.

As would be understood by one skilled in the art, MAX phases arelayered, hexagonal carbides and nitrides having the general formula:M_(n+1)AX_(n), where n=1 to 3, M is an early transition metal, A is anA-group (mostly IIIA and IVA, or groups 13 and 14) element, and X iseither carbon and/or nitrogen. MAX phases suitable for use as solid drylubricants herein include, but are not limited to, Ti₃SiC₂ or Ti₂SnC,which are inert.

Carbon and carbon-based materials suitable for use as solid drylubricants herein include, but are not limited to: diamond, includingdiamond like carbon (DLC) and ultra-nanocrystalline diamond; carbonnanotubes; fluorenes; graphene; graphene oxide; graphite; graphitecomposites, such as Cu-graphite composites; and tetrahedral amorphouscarbon. Such carbon and carbon-based materials may be present within acoating layer or material composition in an amount of at least 5 wt. %,or from 5 to 35 wt. %, or from 10 to 30 wt. %, or from 15 to 25 wt. %,or at most 35 wt. %, each based on the total weight of the coating layeror material composition (by surface). In some such aspects, the distancebetween grains in the microstructure of such carbon-based solidlubricants is comparable to or smaller than that in erosion and abrasiveparticles used in oilfields, such as sand. The material grain size ofsuch carbon-based solid lubricants is smaller than that of sandparticles used in oilfields as erosion and abrasive particles.

Solid dry lubricants may exhibit any of various wear/frictionmechanisms, including: interlayer shear and water intercalation; highchemical inertness and repulsive forces due to hydrogen termination;tribochemically induced surface reaction and termination of top carbonatoms; tribochemically induced reaction with H, O, or OH interlayershear and transfer film formulation; and interlayer shear and preventionof tribocorrosion. Solid dry lubricants may be applied via any ofvarious application methods, including: evaporation, including thermalevaporation; pyrolysis; sputtering, including RF and DC sputtering; ionbeam; chemical vapor deposition (CVD), including plasma enhanced CVD(PECVD), microwave plasma CVD (MPCVD), and hot filament CVD (HFCVD);cathodic arc, pulsed laser, atomic laser deposition (ALD); andexfoliation, including chemical exfoliation and mechanical exfoliation.

Coatings—Multilayer

Certain aspects of the disclosure include multilayer coatings, materialcompositions thereof, apparatus coated therewith, and methods of making,applying, and using the same. In some such aspects, the multilayercoatings, such as coating 210 of FIG. 2, includes at least two distinctlayers. The multilayer coatings disclosed herein may include more thantwo layers. In some aspects, a first layer of the multilayer coating(e.g., layer 216 a in FIG. 2) is the same or substantially the same asthe coating layer described herein with reference to the monolayercoating, or is the same or substantially the same as the continuousbinder phase described herein with reference to the monolayer coating.The first layer may be the innermost layer of the multilayer coating(i.e., the layer positioned closest to the underlying apparatus and notexposed). The first layer may be applied (e.g., onto a surface of theapparatus) via electroplating or electroless plating.

A second layer of the multilayer coating (e.g., layer 216 b in FIG. 2)may be applied over the first layer. Second coating layer 216 b has athickness (thickness 113 in FIG. 2) of at least 2 μm, or from 2 to 40μm, or from 5 to 35 μm, or from 10 to 30 μm, or from 15 to 25 μm, or atmost 40 μm thick. Second coating layer 216 b may contain carbon. In somesuch aspects, second coating layer 216 b contains equal to or greaterthan 30 wt. % C, based on the total weight of second coating layer 216b. The material composition of second coating layer 216 b may be orinclude DLC; a transition-metal carbide compound, such as TiC, Ti(C,N),or WC; or a silicon (non-transition metal) carbide, including amorphousor semi-amorphous.

In some aspects, the multilayer coatings disclosed herein include morethan two layers. With reference to FIG. 6, coated surface 600 onapparatus 614 is depicted, including three-layer coating 610 appliedthereto. Coating 610 includes first layer 616 a applied to surface 612of apparatus 614, which may be the same or similar to first layer 216 a.Coating 610 includes second layer 616 b applied to surface 618 a offirst layer 616 a. Second layer 616 b may be the same or similar tosecond layer 216 b. Coating 610 includes third layer 616 c applied tosurface 618 b of second layer 616 b. In some aspects, third layer 616 cis a solid-lubricant layer, such as a sulfide layer. For example, thematerial composition of third layer 616 c may be or include MOS₂,TiC_(x)S_(y), TiCS/Se/Te, WS₂, or any of the solid dry lubricantsdisclosed herein.

Applications

The material compositions disclosed herein may be applied to thesurfaces of any of various apparatus in the form of a coating or othermaterial construction. The material compositions disclosed herein areparticularly suitable for application to surfaces that are in contactwhile moving relative to one another.

Exemplary parts or apparatus that include surfaces that are in contactand move relative to one another include valves. For example, thepresent material compositions may be applied to one or more surfaces ofa ball valve (e.g., a rotary actuated ball valve), such as on thesurface of a ball of a ball valve, the surface of a seat of a ballvalve, the surface of a bearing of a ball valve, or combinationsthereof. In operation, with the material composition applied to surfacesof a ball valve (e.g., to the ball and/or seat), actuation of the ballvalve (i.e., pivoting of the ball) may be eased in comparison to anotherwise identical ball valve without the material composition appliedthereto. That is, less force (lower torque) is required to be applied tocause the ball to move between the open and closed positions than wouldbe required in an otherwise identical ball valve without the materialcomposition applied thereto. The material composition may also providethe ball valve, when applied thereto, with eliminated or reduced leakageof fluids over time (i.e., reduced leakage of the fluids flowing throughthe ball valve). FIG. 7 depicts an exemplary ball valve 798, includingbearing 796, stem 794, ball 792, seat 790, and body 788. While only ball792 is shown as including coating 710 thereon, other portions of ballvalve 798 may include the coating, such as bearing 796 and seat 790.

Other valves upon which the coatings disclosed herein may be appliedinclude, but are not limited to, downhole valves, such as flow controlvalves, safety valves, formation isolation valves, and subsea lubricatorvalves. In any such valves, the coatings disclosed herein may providefor reduced actuation power (e.g., reduced amount of piston forcerequired to actuate linear control valves). In some such aspects, thecoatings disclosed herein may be applied to sleeve-bearing assemblies(sliding sleeve assemblies) and/or sliding pistons of flow controlvalves, the inner and outer diameters of flow tubes of downhole safetyvalves, or other portions of the valves where surfaces are in contactand move relative to one another. While not specifically shown, oneskilled in the art would understand that apparatus 114, 214, 314 a, 314b, 414 a, 414 b and 614 are representative of portions of any of suchapparatus. As one skilled in the art would understand the components andfunction of such valves, the components of such parts of the operationthereof are not detailed herein.

When applied to surfaces of flow control valves, the coatings mayprovide for lower actuation forces in various corrosive and sandy(abrasive and erosive) operating conditions. For example, the coatingmay be applied to portions of flow control valves, including slidingsleeve assemblies, that are used to control flow downhole (productionand/or injection flow). The coating may be applied to flow controlvalves, including sliding pistons, that are used to adjust flow.

When applied to surfaces of safety valves, the coatings may provide forlower actuation forces, such as in the case of the presence of scaledeposits, as well as providing for the reduced occurrence of corrosion.For example, the coating may be applied to the inner and outer diametersof the flow-tube of a safety valve.

Thus, certain aspects of the present disclosure include a flow controlvalve. The valve includes a first surface movably engaged with a secondsurface (i.e., the surfaces are in contact and move relative to oneanother during operation of the valve). A coating is on the firstsurface, the second surface, or combinations thereof. The coatingincludes at least a first layer. The coating is characterized by: acoefficient of friction of less than 0.15; a hardness in excess of 1,200HVN; impermeability to liquids at pressures ranging from 15 and 20,000psi; a surface finish of 63 or less; and a thickness ranging from 0.5 to20 mils. The coating may be further characterized by: inertness andcorrosion resistance; a bond strength to the first surface of equal toor greater than 10 ksi; or combinations thereof. In one exemplaryembodiment, the present disclosure provides for a flow-control valvethat includes a ball-seat assembly (ball valve), a gate-seat assembly(gate valve), a sleeve-bearing assembly (sliding sleeve), or alinear/rotating piston flow tube-sleeve/housing assembly having at leastone surface that is coated in accordance with the present disclosure,where the surface is a surface that is in contact with at least oneother surface and moves relative to that other surface during operationof the flow-control valve and is characterized by: (1) being amonolayered or multilayered coating; (2) being impermeable to liquid atpressures ranging from 15 to 20,000 psi; (3) having a thickness of from0.5 and 20 mils; (4) having a hardness in excess of 1200 HVN; (5) havinga CoF of less than 0.15, in dry condition; (6) having a surface finishof 63 or less; (7) or combinations thereof.

The present coatings may be applied to any of various surface of partsused in surface, subsea, and downhole drilling operations, includingparts through which corrosive fluids flow or otherwise contact.

Method of Applying Material Compositions to Surfaces

Certain aspects of the present disclosure provide for a method of makingcoated apparatus. In some such aspects, the method includes a sequenceof coating deposition processes or steps that includes: (1) applying afirst layer of the coating via electroplating, electroless plating,thermal spraying, cladding, or applying carbide cloth (e.g., CONFORMACLAD®); and then, (2) applying a second layer of the coating viasputtering, ion beam, PECVD, cathodic arc, CVD, or another thin filmdeposition process. In some such aspects, the sequence includesoptionally performing a surface preparation step to the surface of thefirst layer, after applying the first layer and before applying thesecond layer of the coating. The surface preparation step may includecleaning the surface, honing the surface, polishing the surface, orcombinations thereof. For example, FIGS. 8A-8D depict a coated apparatus800, the same or similar as that shown in FIG. 2, being formed by such asequence of steps. In FIG. 8A, uncoated apparatus 814 is provided.Moving from FIG. 8A to FIG. 8B, first layer 816 a is coated onto surface812 of apparatus 814 via coating application 878, such aselectroplating, electroless plating, thermal spraying, cladding, orapplying carbide cloth. Moving from FIG. 8B to FIG. 8C, surface 818 a issubjected to surface preparation 876, such as cleaning, honing, and/orpolishing. Moving from FIG. 8C to FIG. 8D, second layer 816 b is appliedto surface 818 a via second coating application 874, such as viasputtering, ion beam, PECVD, cathodic arc, CVD, or another thin filmdeposition process. Thus, uncoated apparatus 814 is treated to formcoated apparatus 800, including coating 810 with surface 818 b.

Material Constructions

In some aspects, the present disclosure provides for materialconstructions, whether applied to or in isolation of an underlyingapparatus, including methods of making, applying, and using the same.The material constructions may be the same or substantially the same asthe mono-, bi-, and tri-layer coatings shown and described withreference to FIGS. 1-8D, and may include any number of layers ordiscrete components, such as one, two, three, or more than three. Withreference to FIG. 9, material construction 901 is depicted. Materialconstruction 901 includes three-layers, including first layer 916 a,which may be the same or similar to first layer 616 a; second layer 916b applied to surface 918 a of first layer 916 a, which may be the sameor similar to second layer 616 b; and third layer 916 c applied tosurface 918 b of second layer 916 b, which may be the same or similar tothird layer 616 c.

FIGS. 10A and 10B depict two exemplary, high magnification electronmicrographs. FIG. 10A is a top view showing the surface structure of acoating at the submicron scale, in accordance with the presentdisclosure, and FIG. 10B is a side view, cross-section of the coating ofFIG. 10A showing the two layers of the coating.

Although the present embodiments and advantages have been described indetail, it should be understood that various changes, substitutions andalterations can be made herein without departing from the spirit andscope of the disclosure. Moreover, the scope of the present applicationis not intended to be limited to the particular embodiments of theprocess, machine, manufacture, composition of matter, means, methods andsteps described in the specification. As one of ordinary skill in theart will readily appreciate from the disclosure, processes, machines,manufacture, compositions of matter, means, methods, or steps, presentlyexisting or later to be developed that perform substantially the samefunction or achieve substantially the same result as the correspondingembodiments described herein may be utilized according to the presentdisclosure. Accordingly, the appended claims are intended to includewithin their scope such processes, machines, manufacture, compositionsof matter, means, methods, or steps.

What is claimed is:
 1. A material construction comprising: a first layerincluding at least two immiscible phases, including from 70 to 99 volumepercent of a continuous phase and from 1 to 30 volume percent of adiscontinuous phase dispersed within the continuous phase, each based ona total volume of the first layer; wherein the discontinuous phasecomprises a solid dry lubricant, and wherein the continuous phasecomprises a transition-metal.
 2. The material construction of claim 1,wherein the continuous phase has a face-centered cubic structure,wherein the continuous phase comprises Ni, Co, Cr, Mo, W, Fe, orcombinations thereof.
 3. The material construction of claim 2, whereinthe continuous phase comprises Ni and Co in an amount ranging from 50 to70 wt. %, Cr in an amount ranging from 16 wt. % to 30 wt. %, Mo in anamount ranging from 2.5 wt. % to 10 wt. %, W in an amount ranging from 0wt. % to 4 wt. %, and Fe in an amount ranging from 0 wt. % to 15 wt. %,each based on a total weight of the continuous phase.
 4. The materialconstruction of claim 2, wherein the composition of the continuous phasesatisfies the following pitting resistance equivalent number value rule:1 wt. % Cr+3.3% Mo+0.5% W+16N≥30.
 5. The material construction of claim1, wherein particles of the discontinuous phase have a particle sizeranging from 0.5 to 150 μm and an aspect ratio of from 1 to
 100. 6. Thematerial construction of claim 1, wherein the solid lubricant comprisesone of a soft metal, a transition metal dichalcogenide, a binary oxide,a ternary oxide, an alkaline-earth fluoride, boron nitride, a MAX phase,carbon, or a carbon-based material.
 7. The material construction ofclaim 6, wherein the solid dry lubricant comprises Ag, Pb, Au, In, Cu,MoS₂, WS₂, MoSe₂, PBO, MoO₃, WO₃, CuO, V₂O₅, Re₂O7, B₂0₃, Al₂O₃, ZrO₂,Fe₂0₃, FeO, MgO, Ag₂MoO₄, Ag₂WO₄, Ag₃VO₄, CaF₂, BaF₂, hexagonal boronnitride , Ti₃SiC₂, Ti₂SnC, diamond, diamond like carbon,ultra-nanocrystalline diamond, carbon nanotubes, fluorenes, graphene,graphene oxide, graphite, graphite composite, or tetrahedral amorphouscarbon.
 8. The material construction of claim 1, further comprising asecond layer applied over a surface of the first layer, wherein thesecond layer comprises at least 30 wt. % carbon.
 9. The materialconstruction of claim 8, wherein the second layer is deposited usingelectroplating, electroless plating, thermal spraying, cladding,sputtering, ion beam, plasma enhanced chemical vapor deposition,cathodic arc, or chemical vapor deposition.
 10. The materialconstruction of claim 8, further comprising a third layer applied over asurface of the second layer, wherein the third layer includes a solidlubricant layer.
 11. The material construction of claim 10, wherein thethird layer comprises a sulfide.
 12. The material construction of claim11, wherein the third layer comprises MOS₂, TIC_(X)S_(Y), TiCS/Se/Te, orWS₂.
 13. The material construction of claim 1, wherein the first layeris deposited using electroplating, electroless plating, thermalspraying, or cladding.
 14. The material construction of claim 13,wherein a second layer is deposited on a surface of the first layerusing electroplating, electroless plating, thermal spraying, cladding,sputtering, ion beam, plasma enhanced chemical vapor deposition,cathodic arc, or chemical vapor deposition.
 15. A material constructioncomprising: a coating comprising at least a first layer, wherein thecoating is characterized by: a coefficient of friction of less than0.15; a hardness in excess of 1,200 HVN; impermeability to liquids atpressures ranging from 15 and 20,000 psi; a surface finish of 63 orless; and a thickness ranging from 0.5 to 20 mils, and wherein the firstlayer includes at least two immiscible phases, including from 70 to 99volume percent of a continuous phase and from 1 to 30 volume percent ofa discontinuous phase dispersed within the continuous phase, wherein thediscontinuous phase comprises a solid dry lubricant, and wherein thecontinuous phase comprises a transition-metal.
 16. The materialconstruction of claim 15, further comprising a second layer applied overa surface of the first layer, wherein the second layer comprises atleast 30 wt. % carbon.
 17. The material construction of claim 16,further comprising a third layer applied over a surface of the secondlayer, wherein the third layer includes a solid lubricant layer.
 18. Thematerial construction of claim 17, wherein the coating is applied to apart used in an operation that includes a corrosive fluid.
 19. Thematerial construction of claim 18, wherein the operation is one of asubsea operation, a surface operation, or a downhole drilling operation.20. A material construction comprising: a first layer including at leasttwo immiscible phases, including from 70 to 99 volume percent of acontinuous phase and from 1 to 30 volume percent of a discontinuousphase dispersed within the continuous phase, each based on a totalvolume of the first layer, wherein the discontinuous phase comprises asolid dry lubricant, and wherein the continuous phase comprises atransition-metal, and wherein the first layer is deposited usingelectroplating, electroless plating, thermal spraying, or cladding; asecond layer applied over a surface of the first layer, wherein thesecond layer comprises at least 30 wt. % carbon, wherein the secondlayer is deposited using electroplating, electroless plating, thermalspraying, cladding, sputtering, ion beam, plasma enhanced chemical vapordeposition, cathodic arc, or chemical vapor deposition.; and a thirdlayer applied over a surface of the second layer, wherein the thirdcomprises MOS₂, TIC_(X)S_(Y), TiCS/Se/Te, or WS₂.
 21. The materialconstruction of claim 18, wherein the continuous phase comprises Ni andCo in an amount ranging from 50 to 70 wt. %, Cr in an amount rangingfrom 16 wt. % to 30 wt. %, Mo in an amount ranging from 2.5 wt. % to 10wt. %, W in an amount ranging from 0 wt. % to 4 wt. %, and Fe in anamount ranging from 0 wt. % to 15 wt. %, each based on a total weight ofthe continuous phase.
 22. The material construction of claim 19, whereinthe solid dry lubricant comprises Ag, Pb, Au, In, Cu, MoS2, WS2, MoSe2,PBO, MoO3, WO3, CuO, V2O5, Re2O7, B203, Al2O3, ZrO2, Fe203, FeO, MgO,Ag2MoO4, Ag2WO4, Ag3VO4, CaF2, BaF2, hexagonal boron nitride, Ti3SiC2,Ti2SnC, diamond, diamond like carbon, ultra-nanocrystalline diamond,carbon nanotubes, fluorenes, graphene, graphene oxide, graphite,graphite composite, or tetrahedral amorphous carbon.
 23. The materialconstruction of claim 22, wherein the coating is applied to a part usedin an operation that includes a corrosive fluid.
 24. The materialconstruction of claim 23, wherein the operation is one of a subseaoperation, a surface operation, or a downhole drilling operation.